Liquid crystalline medium and liquid crystal display

ABSTRACT

A dielectrically positive liquid crystalline media comprising: 
 
a first dielectrically positive component, component A, comprising a dielectrically neutral compound of formula I  
                 
wherein the parameters have the meanings defined herein; a second dielectrically positive component, component B, comprising one or more dielectrically positive compounds having a dielectric anisotropy of more than 3; and optionally a dielectrically neutral component, component C, comprising one or more dielectrically neutral compounds having a dielectric anisotropy in the range from −1.5 to 3, are suitable for use in liquid crystal displays, especially active matrix displays, and in particular TN and to IPS displays.

FIELD OF THE INVENTION

The present invention relates to liquid crystalline media and to liquidcrystal displays comprising these media, especially to displaysaddressed by an active matrix and in particular to displays of thetwisted nematic or of the in plane switching type.

STATE OF THE ART AND PROBLEM TO BE SOLVED

Liquid Crystal Displays (LCDs) are widely used to display information.LCDs are used for direct view displays, as well as for projection typedisplays. Electro-optical modes employed are, e.g., the twisted nematic(TN)-, the super twisted nematic (STN)-, the optically compensated bend(OCB)- and the electrically controlled birefringence (ECB)-mode withtheir various modifications, as well as others. All these modes use anelectrical field, which is substantially perpendicular to thesubstrates, respectively to the liquid crystal layer. Besides thesemodes there are also electro-optical modes employing an electrical fieldsubstantially parallel to the substrates, respectively the liquidcrystal layer, like, e.g., the In-Plane Switching mode (as disclosed,e.g., in DE 40 00 451 and EP 0 588 568). Especially, thiselectro-optical mode is used for LCDs for modern desktop monitors and isenvisaged to be applied for displays for multi media applications. Theliquid crystals according to the present invention are preferably usedin this type of displays.

For these displays new liquid crystalline media with improved propertiesare required. Especially the response times have to be improved for manytypes of applications. Thus, liquid crystalline media with lowerviscosities (η), especially with lower rotational viscosities (γ₁) arerequired. In practical liquid crystalline media the rotational viscosityis correlated both with the threshold voltage and the operation voltageof the media. Thus, the rotational viscosity preferably should, e.g.,for a medium with a clearing point of about 75° C. and a thresholdvoltage of about 2.0 V be 75 mPa·s or less, preferably 60 mPa·s or less,and especially 55 mPa·s or less. Besides this parameter, the media haveto exhibit a suitably wide range of the nematic phase, an appropriatebirefringence (Δn) and dielectric anisotropy (Δε) should be high enoughto allow a reasonably low operation voltage. Preferably, Δε should behigher than 4 and very preferably higher than 5, preferably, however,not higher than 15 and in particular not higher than 12, as this wouldbe detrimental for an at least reasonably high specific resistivity.

The displays according to the present invention are preferably addressedby an active matrix (active matrix LCDs, short AMDs), preferably by amatrix of thin film transistors (TFTs). However, the inventive liquidcrystals can also beneficially be used in displays with other knownaddressing means.

There are various different display modes using composite systems ofliquid crystal materials of low molecular weight together with polymericmaterials. These are, e.g., polymer dispersed liquid crystal (PDLC)-,nematic curvilinearily aligned phase (NCAP)- and polymer network(PN)-systems, as disclosed, for example, in WO 91/05 029 or axiallysymmetric microdomain (ASM) systems and others. In contrast to these,the modes especially preferred according to the instant invention areusing the liquid crystal medium as such, oriented on surfaces. Thesesurfaces typically are pre-treated to achieve uniform alignment of theliquid crystal material. The display modes according to the instantinvention preferably use an electrical field substantially parallel tothe composite layer.

Liquid crystal compositions suitable for LCDs and especially for IPSdisplays are known, e.g., from JP 07-181 439 (A), EP 0 667 555, EP 0 673986, DE 195 09 410, DE 195 28 106, DE 195 28 107, WO 96/23 851 and WO96/28 521. These compositions, however, do have significant drawbacks.Most of them, amongst other deficiencies, lead to unfavorably longresponse times, have too low values of the resistivity and/or requireoperation voltages, which are too high. Further, many of the existingliquid crystal material are not particularly stable under storage at lowtemperatures.

Thus, there is a significant need for liquid crystalline media withsuitable properties for practical applications such as a wide nematicphase range, appropriate optical anisotropy Δn, according to the displaymode used, a high Δε, and especially low viscosities.

SUMMARY OF THE INVENTION

Surprisingly, it now has been found that liquid crystalline media with asuitably high Δε, a suitable phase range, and Δn can be realized, whichdo not exhibit the drawbacks of the materials of the prior art or atleast do exhibit them to a significantly lesser degree.

Upon further study of the specification and appended claims, furtheraspects and advantages of this invention will become apparent to thoseskilled in the art.

These improved liquid crystalline media according to the instantapplication comprise at least the following components:

-   -   a first dielectrically positive component, component A,        comprising a dielectrically positive compound of formula I    -   wherein    -   R¹ is alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy        with 1 to 7 C-atoms or alkenyl, alkenyloxy, alkoxyalkyl, or        fluorinated alkenyl with 2 to 7 C-atoms, and preferably is alkyl        or alkenyl, most preferably alkyl,    -   X¹ is halogen, preferably Cl or F and most preferably Cl,    -   L are independently of each other, Cl or F, preferably F, and    -   n and m are, independently of each other, each an integer from 0        to 4, preferably 0, 1 or 2 and most preferably one of them is 1        and the other one is 0,    -   a second dielectrically positive component, component B,        comprising one or more dielectrically positive compounds having        a dielectric anisotropy of more than 3, and    -   optionally a dielectrically neutral component, component C,        comprising one or more dielectrically neutral compounds having a        dielectric anisotropy in the range from −1.5 to 3.

Preferably, the concentration of component A in the medium is 0.1% to20%, more preferably 0.5% to 15%, even more preferably 1% to 10% andmost preferably from 1.5% to 8%.

Preferably, the first dielectrically positive component, component A,comprises, more preferably consists predominantly of, even morepreferably consists essentially, and most preferably consists entirelyof dielectrically positive compounds of formula Ia

wherein

-   R¹ and X¹ have the respective meanings given under formula I above,    and-   one of L¹¹ and L¹² is F and the other one is H.

The isotropic refractive index (n_(iso)) of the compounds of formula Iapreferably used according to the instant invention is 1.57 or more. Theisotropic refractive index (n_(iso)) is calculated asn_(iso),=(n_(e)+2n_(o))/3 from the refractive indices n_(e) and n_(o)extrapolated from a solution of 10% of the compound of interest inZLI-4792.

Especially preferred are compounds of formula I selected from thesub-formulae Ia-1 to Ia-4

wherein

-   R¹ has the meaning given under formula I above.

Preferably, the second dielectrically positive component, component B,comprises, more preferably consists predominantly of, even morepreferably consists essentially, and most preferably it consistsentirely of dielectrically positive compounds having a dielectricanisotropy of more than 3.

Preferably, this component, component B, comprises, more preferablyconsists predominantly of, even more preferably consists essentially,and most preferably consists entirely of one or more dielectricallypositive compounds having a dielectric anisotropy of more than 3,selected from formulae II and III

wherein

-   R² and R³, independently of each other, are alkyl, alkoxy,    fluorinated alkyl or fluorinated alkoxy with 1 to 7 C-atoms,    alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl with 2 to 7    C-atoms, and R² and R³ preferably are alkyl or alkenyl,    are, independently of each other,-   L²¹, L²², L³¹ & L³², are, independently of each other, H or F,    preferably L²¹ and/or L³¹ is F,-   X² and X³ are, independently of each other, halogen, halogenated    alkyl or halogenated alkoxy with 1 to 3 C-atoms or halogenated    alkenyl or alkenyloxy with 2 or 3 C-atoms, preferably F, Cl, —OCF₃    or —CF₃, most preferably F, Cl or —OCF₃,-   Z³ is —CH₂CH₂—, —CF₂CF₂—, —COO—, trans- —CH═CH—, trans- —CF═CF—,    —CH₂O— or a single bond, preferably —CH₂CH₂—, —COO—, trans- —CH═CH—    or a single bond and most preferably —COO—, trans- —CH═CH—, trans-    or a single bond, and-   l, m, n and o are, independently of each other, 0 or 1.

In a preferred embodiment of the present invention component B,comprises, more preferably consists predominantly of, even morepreferably consists essentially, and most preferably consists entirelyof one or more dielectrically positive compounds having a dielectricanisotropy of more than 3, selected from formulae II-1 and II-2

wherein the parameters have the respective meanings given under formulaII above and in Formula II-1 and the parameters L²³ and L²⁴ are,independently of each other and of the other parameters, H or F.

Preferably, component B comprises compounds selected from the group ofcompounds of formulae II-1 and II-2, wherein L²¹ and L²² and/or L²³ andL²⁴ are both F

In a preferred embodiment component B comprises compounds selected fromthe group of compounds of formulae II-1 and II-2, wherein L²¹, L²², L²³and L²⁴ all are F.

Preferably, component B comprises one or more compounds of formula II-1.Preferably, the compounds of formula II-1 are selected from the group ofcompounds of formulae II-1a to II-1i

wherein the parameters have the respective meanings given above.

Preferably, component B comprises compounds selected from the group ofcompounds of formulae II-1a to II-1e wherein L²¹ and L²² and/or L³¹ andL³² are both F

In a preferred embodiment component B comprises compounds selected fromthe group of compounds of formulae II-1a to II-1e, wherein L²¹, L²², L³¹and L³² all are F.

Especially preferred compounds of formula II-1 are

wherein the R² has the meaning given above.

Preferably, Component B comprises one or more compounds of formula II-2.Preferably, the compounds of formula II-2 are selected from the group ofcompounds of formulae II-2a to II-2d

wherein the parameters have the respective meanings given above andpreferably

-   L²¹ and L²² are both F and L³¹ and L³², are both H or-   L²¹, L²², L³¹ and L³² are all F

Especially preferred compounds of formula II-2 are

wherein the R² has the meaning given above.

In a further preferred embodiment of the present invention component B,comprises, more preferably consists predominantly of, even morepreferably consists essentially of, and most preferably consistsentirely of one or more dielectrically positive compounds having adielectric anisotropy of more than 3, selected from the group offormulae III-1 and III-2

wherein the parameters have the respective meanings given under formulaIII above.

Preferably, component B comprises one or more compounds of formulaIII-1. Preferably, the compounds of formula III-1 are selected from thegroup of compounds of formulae III-1a and III-1b

wherein the parameters have the respective meanings given above and theparameters L³³ and L³⁴ are, independently of each other and of the otherparameters, H or F.

Preferably, component B comprises one or more compounds of formulaIII-2. Preferably, the compounds of formula III-2 are selected from thegroup of compounds of formulae III-2a to III-2h

wherein the parameters have the respective meanings given above, and L³⁵and L³⁶ are, independently of each other and the other parameters, H orF.

Preferably, component B comprises one or more compounds of formulaIII-1a, which preferably are selected from the group of compounds offormulae III-1a-1 to III-1a-6

wherein the R³ has the meaning given above.

Preferably, component B comprises one or more compounds of formulaIII-2a, which are preferably selected from the group of compounds offormulae III-2a-1 to III-2a-4

wherein the R³ has the meaning given above.

Preferably, component B comprises one or more compounds of formulaIII-2b, which are preferably selected from the group of compounds offormulae III-2b-1 to III-2b-6

wherein the R³ has the meaning given above.

Preferably, component B comprises one or more compounds selected fromthe group of compounds of formulae III-2c and III-2d, which arepreferably selected from the group of compounds of formulae III-2c-1 andIII-2d-1

wherein the R³ has the meaning given above.

Preferably, component B comprises one or more compounds of formulaIII-2e, which are preferably selected from the group of compounds offormulae III-2e-1 to III-2e-5

wherein the R³ has the meaning given above.

Preferably, component B comprises one or more compounds of formulaIII-2f, which are preferably selected from the group of compounds offormulae III-2f-1 to III-2f-5

wherein the R³ has the meaning given above.

Preferably, component B comprises one or more compounds of formulaIII-2g, which are preferably selected from the group of compounds offormulae III-2g-1 to III-2g-3

wherein the R³ has the meaning given above.

Preferably, component B comprises one or more compounds of formulaIII-2h, which are preferably selected from the group of compounds offormulae III-2h-1 to III-2h-3

wherein the R³ has the meaning given above.

Alternatively or additionally to compounds of formulae III-1 and/orIII-2 the media according to the present invention may comprise one ormore compounds of formula III-3

wherein the parameters have the respective meanings given under formulaIII above, and preferably of formula III-3a

wherein the R³ has the meaning given above.

Preferably, the liquid crystalline media according to the presentinvention comprise a dielectrically neutral component, component C. Thiscomponent has a dielectric anisotropy in the range from −1.5 to 3.Preferably, component C comprises, preferably consists predominantly of,preferably consists essentially of, and especially preferably consistsentirely of dielectrically neutral compounds, having a dielectricanisotropy in the range from −1.5 to 3. Preferably, this componentcomprises one or more, more preferably comprises predominantly of, morepreferably consists essentially of, and especially preferably consistsentirely of dielectrically neutral compounds, having a dielectricanisotropy in the range from −1.5 to 3, of formula IV

wherein

-   compounds of formula I are excluded from formula IV,-   R⁴¹, and R⁴², independently of each other have the meaning given for    R² under formula II above, preferably R⁴¹ is alkyl and R⁴² is    alkoxy,-   independently of each other, and in case-   is present twice, also these, independently of each other, are-   preferably at least one of-   Z⁴¹ and Z⁴² are, independently of each other, and in case Z⁴¹ is    present twice, also these independently of each other, —CH₂CH₂—,    —COO—, trans- —CH═CH—, trans- —CF═CF—, —CH₂O—, —CF₂O— or a single    bond, preferably at least one of them is a single bond, and-   p is 0, 1 or 2, preferably 0 or 1.

Preferably, the dielectrically neutral component, component C, comprisesone or more compounds selected from the group of compounds of formulaeIV-1 to IV-6

wherein compounds of formula I are excluded from formula IV-1, R⁴¹ andR⁴² have the respective meanings given under formula IV above, and informulae IV-1, IV4 and IV-5 R⁴¹ preferably is alkyl or alkenyl,preferably alkenyl and R⁴² preferably is alkyl or alkenyl, preferablyalkyl, in formula IV-2 R⁴¹ and R⁴² preferably are alkyl, and in formulaIV-3 R⁴¹ preferably is alkyl or alkenyl, preferably alkyl and R⁴²preferably is alkyl or alkoxy, preferably alkoxy.

Preferably, the dielectrically neutral component, component C, comprisesone or more compounds selected from the group of compounds of formulaeIV-1, IV-3, IV-4 and IV-5, preferably one or more compounds of formulaIV-1 and one or more compounds selected from the group of formulae IV-3and IV-4, preferably one or more compounds each of formulae IV-1, IV-3and IV-4 and most preferably one or more compounds each of formulaeIV-1, IV-3, IV-4 and IV-5.

Preferably, the dielectrically neutral component, component C, comprisesone or more compounds selected from the group of compounds of formulaeIV-1a, IV-1b, IV-4a, and IV-4b, IV-6a and IV-6b

wherein

-   R is alkyl with 1 to 5, preferably with 1 to 3 C-atoms,-   R′ is H or alkyl with 1 to 3, preferably with 1 to 2 C-atoms,    preferably H or methyl and-   R″ is H or alkyl with 1 to 3, preferably with 1 to 2 C-atoms,    preferably H.

In a further preferred embodiment of the present invention, which may bepart of the previously described embodiments or a different one, theliquid crystal mixtures according to the present invention comprisecomponent C, comprising, preferably predominantly consisting of, morepreferably consisting essentially of, and most preferably entirelyconsisting of compounds of formula IV selected from the group ofcompounds of formulae IV-1 to IV-6, as shown above, and optionally offormulae IV-7 to IV-14

wherein

-   R⁴¹ and R⁴² are, independently of each other, alkyl, alkoxy,    fluorinated alkyl or fluorinated alkoxy with 1 to 7 C-atoms,    alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl with 2 to 7    C-atoms and-   L⁴ is H or F.

Alternatively or additionally to compounds of formulae II and/or III,the media according to the present invention may comprise one or moredielectrically positive compounds of formula V

wherein

-   R⁵ is alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy with 1    to 7 C-atoms, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated    alkenyl with 2 to 7 C-atoms, and R¹ preferably is alkyl or alkenyl,    are, independently of each other,-   L⁵¹ and L⁵², are, independently of each other, H or F, preferably    L⁵¹ is F and-   X⁵ is halogen, halogenated alkyl or alkoxy with 1 to 3 C-atoms or    halogenated alkenyl or alkenyloxy with 2 or 3 C-atoms, preferably F,    Cl, —OCF₃ or —CF₃, most preferably F, Cl or —OCF₃,-   Z⁵ is —CH₂CH₂—, —CF₂CF₂—, —COO—, trans- —CH═CH—, trans- —CF═CF— or    —CH₂O, preferably —CH₂CH₂—, —COO— or trans- —CH═CH— and most    preferably —COO— or —CH₂CH₂—, and-   q is 0or 1.

Preferably, the media according to the present invention comprises oneor more compounds of formula V, preferably selected from the group ofcompounds of formulae V-1 and V-2

wherein the parameters have the respective meanings given above and theparameters L⁵³ and L⁵⁴ are, independently of each other and of the otherparameters, H or F and preferably Z⁵ is —CH₂—CH₂—.

Preferably, the compounds of formula V-1 are selected from the group ofcompounds of formulae V-1a and V-1b

wherein the R⁵ has the meaning given above.

Preferably, the compounds of formula V-2 are selected from the group ofcompounds of formulae V-2a to V-2d

wherein the R⁵ has the meaning given above.

Preferably, the liquid crystalline media according to the presentinvention comprise an additional dielectrically neutral component,component D. This component has a dielectric anisotropy in the rangefrom −1.5 to 3. Preferably, component D comprises, preferably consistspredominantly of, preferably consists essentially of, and especiallypreferably consists entirely of dielectrically neutral compounds, havinga dielectric anisotropy in the range from −1.5 to 3. Preferably, thiscomponent comprises one or more, more preferably consists predominantlyof, more preferably consists essentially of, and especially preferablyconsists entirely of dielectrically neutral compounds, having adielectric anisotropy in the range from −1.5 to 3, of formula VI

wherein

-   R⁶¹, and R⁶², independently of each other have the meaning given for    R² under formula II above, preferably R⁶¹ is alkyl and R⁶² is alkyl    or alkenyl,    and in case it is occurring twice in each occurrence independently    of each other, is    -   preferably at least one of-   Z⁶¹ and Z⁶² are, independently of each other, and in case Z⁶¹ is    present twice, also these independently of each other, —CH₂CH₂—,    —COO—, trans- —CH═CH—, trans- —CF═CF—, —CH₂O—, —CF₂O— or a single    bond, preferably at least one of them is a single bond, and-   r is 0, 1 or 2, preferably 0 or 1.

Preferably, the dielectrically neutral component, component D, comprisesone or more compounds selected from the group of compounds of formulaeVI-1 and VI-2

wherein R⁶¹ and R⁶² have the respective meanings given under formula VIabove, and R⁶¹ preferably is alkyl, and in formula VI-1 R⁶² preferablyis alkenyl, preferably —(CH₂)₂—CH═CH—CH₃, and in formula VI-2 R⁶²preferably is alkyl.

Preferably, the dielectrically neutral component, component D, comprisesone or more compounds selected from the group of compounds of formulaeVI-1 and VI-2 wherein preferably R⁶¹ is n-alkyl and in formula VI-1 R⁶²preferably is alkenyl and in formula VI-2 R⁶² preferably is n-alkyl.

Preferably, the liquid crystal mixtures according to the presentinvention do contain at least one further component besides components Aand B. This third component may be either one of components C and D,preferably the third component present is component C.

Obviously the mixtures according to the present invention also cancontain all four components A, B, C and D.

Additionally, the liquid crystal mixtures according to the presentinvention may comprise a further optional component, component E, whichhas a negative dielectric anisotropy and comprises, preferablypredominantly consists of, more preferably essentially consists of, andmost preferably entirely consists of dielectrically negative compoundspreferably of formula VII

wherein

-   R⁷¹ and R⁷² independently of each other have the meaning given for    R² under formula II above,-   Z⁷¹ and Z⁷² are, independently of each other, —CH₂CH₂—, —COO—,    trans- CH═CH—, trans- —CF═CF—, —CH₂O—, —CF₂O— or a single bond,    preferably at least one of them is a single bond and most preferably    both are a single bond,-   L⁷¹ and L⁷² are, independently of each other, C—F or N, preferably    at least one of them is C—F and most preferably both of them are C—F    and-   k is 0 or 1.

Preferably, the liquid crystalline media according to the instantinvention comprise, preferably predominantly consist of, more preferablyconsists essentially of, and most preferably entirely consist ofcomponents A to E and in particular of compounds selected from the groupof compounds of formulae I to VII.

Comprising in this application means in the context of compositions thatthe entity referred to, e.g., the medium or the component, contains thecomponent or components or of the compound or compounds in question,preferably in a total concentration of 10% or more and most preferablyof 20% or more.

Predominantly consisting of, in this context, means that the entityreferred to contains 55% or more, preferably 60% or more and mostpreferably 70% or more of the component or components or of the compoundor compounds in question.

Essentially consisting of, in this context, means that the entityreferred to contains 80% or more, preferably 90% or more and mostpreferably 95% or more of the component or components or of the compoundor compounds in question.

Entirely consisting of, in this context, means that the entity referredto contains 98% or more, preferably 99% or more and most preferably100.0% of the component or components or of the compound or compounds inquestion.

Component E preferably comprises, preferably predominantly consists ofand most preferably entirely consists of one or more compounds offormula VII, preferably selected from the group of compounds of formulaeVII-1 to VII-3

wherein

-   R⁷¹ and R⁷² have the respective meanings given under formula VI    above.

In formulae VII-1 to VII-3, R⁷¹ preferably is n-alkyl or 1-E-alkenyl andR⁷² preferably is n-alkyl or alkoxy.

Also other mesogenic compounds, which are not explicitly mentionedabove, can optionally and beneficially be used in the media according tothe instant invention. Such compounds are known to the expert in thefield.

The liquid crystal media according to the instant invention aregenerally characterized by a clearing point of 60° C. or more,preferably of 70° C. or more, more preferably of 75° C. or more, and inparticular of 80° C. or more.

The Δn, at 589 nm (Na^(D)) and 20° C., of the liquid crystal mediaaccording to the instant invention preferably is in the range of 0.060or more to 0.160 or less, more preferably in the range of 0.070 or moreto 0.125 or less, and most preferably in the range of 0.080 or more to0.115 or less.

The Δε, at 1 kHz and 20° C., of the liquid crystal medium according tothe invention preferably is 3.0 or more, more preferably is 4.0 or more.

Preferably, the nematic phase of the inventive media extends at leastfrom 0° C. or less to 70° C. more, more preferably at least from −20° C.or less to 70° C. more, most preferably at least from −30° C. or less to75° C. more, and in particular at least from −40° C. or less to 75° C.more.

In a first preferred embodiment of the present invention the Δn of theliquid crystal media is in the range of 0.110 or more to 0.140 or less,more preferably in the range of 0.115 or more to 0.135 or less, and mostpreferably in the range of 0.120 or more to 0.130 or less, whereas Δεpreferably is in the range from 4.0 or more to 7.0 or less. In thisembodiment the media preferably comprise one or more compounds offormula II and/or of formula III-2f and/or they preferably do notcontain biphenyl compounds with a terminal CF₃ group or a terminal OCF₃group and/or have a clearing point of 60° C. or more.

In a second preferred embodiment of the present invention the Δn of theliquid crystal media is in the range of 0.085 or more to 0.125 or less,more preferably in the range of 0.090 or more to 0.120 or less, and mostpreferably in the range of 0.095 or more to 0.115 or less, whereas Δεpreferably is 5.0 or more, preferably is 6.0 or more, more preferably7.0 or more, even more preferably 8.0 or more, and most preferably inthe range from 5.0 or more to 12.0 or less.

In this embodiment preferably the nematic phase of the inventive mediaextends at least from −20° C. or less to 70° C. more, more preferably atleast from −20° C. or less to 70° C. more, most preferably at least from−30° C. or less to 70° C. more, and in particular at least from −40° C.or less to 70° C. more.

In a third preferred embodiment of the present invention the Δn of theliquid crystal media is in the range of 0.070 or more to 0.120 or less,more preferably in the range of 0.075 or more to 0.115 or less, and mostpreferably in the range of 0.080 or more to 0.110 or less, whereas Δεpreferably is 4.0 or more, more preferably is in the range from 4.0 ormore to 14.0 or less, and most preferably either in the range from 4.0or more to 12.0 or less or, particularly preferred in the range from 6.0or more to 11.0 or less.

In this embodiment preferably the nematic phase of the inventive mediaextends at least from −20° C. or less to 75° C. more, more preferably atleast from −30° C. or less to 70° C. more, most preferably at least from−30° C. or less to 75° C. more, and in particular at least from −30° C.or less to 80° C. more.

Preferably, the storage stability of the inventive media at atemperature of −20° C. in the bulk (LTS_(bulk)) is 120 h or more, morepreferably 500 h, or more and most preferably 1,000 h or more.

More preferably the storage stability of the inventive media at atemperature of −30° C. in the bulk (LTS_(bulk)) is 120 h or more, morepreferably 500 h or more, and most preferably 1,000 h or more.

Most preferably the storage stability of the inventive media at atemperature of −40° C. in the bulk (LTS_(bulk)) is 120 h or more, morepreferably 250 h or more, and most preferably 500 h or more.

The storage stability of the inventive media at a temperature of −20°C., more preferably at a temperature of −30° C., and most preferably ata temperature of −40° C., in the bulk (LTS_(cell)) is preferably 250 hor more, more preferably 500 h, or more and most preferably 1,000 h ormore.

The relative change of the concentration of PUQU-2-F after the “seed”test is preferably 15% or less, more preferably 8% or less, even morepreferably 3% or less, and most preferably 0.1% or less.

The relative change of the concentration of PUQU-3-F after the “seed”test is preferably 10% or less, more preferably 5% or less, even morepreferably 3% or less, and most preferably 0.1% or less.

Component A preferably is used in a concentration from 1% to 15%, morepreferably from 2% to 10%, more preferably from 2% to 8%, and mostpreferably from 3% to 7% of the total mixture.

Component B preferably is used in a concentration from 10% to 70%, morepreferably from 15% to 65, more preferably from 20% to 60%, and mostpreferably from 30% to 50% of the total mixture.

Component C preferably is used in a concentration from 15% to 85%, morepreferably from 30% to 80%, more preferably from 35% to 70%, and mostpreferably from 40% to 60% of the total mixture.

Component D preferably is used in a concentration from 0% to 40%,preferably from 0% to 30%, more preferably from 0% to 20%, and mostpreferably from 4% to 15% of the total mixture.

Component E preferably is used in a concentration from 0% to 30%,preferably from 0% to 15%, and most preferably from 1% to 10% of thetotal mixture.

Optionally, the inventive media can comprise further liquid crystalcompounds in order to adjust the physical properties. Such compounds areknown to the expert. Their concentration in the media according to theinstant invention is preferably 0% to 30%, more preferably 0% to 20%,and most preferably 1% to 15%.

Preferably, the liquid crystal media contain 50% to 100%, morepreferably 70% to 100% and most preferably 80% to 100% and in particular90% to 100% totally of components A, B, C and D, preferably ofcomponents A, B and C, which, in turn, contain, preferably predominantlyconsist of and most preferably entirely consist of one or more ofcompounds of formulae I, II, III, IV, V, VI and VII, preferably offormulae I, II, III, IV, V and VI, respectively.

In the present application the term dielectrically positive meanscompounds or components with Δε>3.0, dielectrically neutral with−1.5≦Δε3.0, and dielectrically negative with Δε<−1.5. Δε is determinedat a frequency of 1 kHz and at 20° C. The dielectric anisotropy of therespective compound is determined from the results of a solution of 10%of the respective individual compound in a nematic host mixture. In casethe solubility of the respective compound in the host mixture is lessthan 10%, the concentration is reduced to 5%. The capacities of the testmixtures are determined both in a cell with homeotropic and withhomogeneous alignment. The cell gap of both types of cells isapproximately 20 μm. The voltage applied is a rectangular wave with afrequency of 1 kHz and a root mean square value typically of 0.5 V to1.0 V; however, it is always selected to be below the capacitivethreshold of the respective test mixture.

For dielectrically positive compounds the mixture ZLI-4792 and fordielectrically neutral, as well as for dielectrically negativecompounds, the mixture ZLI-3086, both of Merck KGaA, Germany are used ashost mixture, respectively. The dielectric permittivities of thecompounds are determined from the change of the respective values of thehost mixture upon addition of the compounds of interest. The values areextrapolated to a concentration of the compounds of interest of 100%.

Components having a nematic phase at the measurement temperature of 20°C. are measured as such, all others are treated like compounds.

The term threshold voltage refers in the instant application to theoptical threshold and is given for 10% relative contrast (V₁₀) and theterm saturation voltage refers to the optical saturation and is givenfor 90% relative contrast (V₉₀) both, if not explicitly statedotherwise. The capacitive threshold voltage (V₀), also calledFreedericksz-threshold (V_(Fr)) is only used if explicitly mentioned.

The ranges of parameters given in this application are all including thelimiting values, unless explicitly stated otherwise.

Throughout this application, unless explicitly stated otherwise, allconcentrations are given in mass percent and relate to the respectivecomplete mixture, all temperatures are given in degrees centigrade(Celsius) and all differences of temperatures in degrees centigrade. Allphysical properties have been and are determined according to “MerckLiquid Crystals, Physical Properties of Liquid Crystals”, StatusNovember 1997, Merck KGaA, Germany and are given for a temperature of20° C., unless explicitly stated otherwise. The optical anisotropy (Δn)is determined at a wavelength of 589.3 nm. The dielectric anisotropy(Δε) is determined at a frequency of 1 kHz. The threshold voltages, aswell as all other electro-optical properties have been determined withtest cells prepared at Merck KGaA, Germany. The test cells for thedetermination of Δε had a cell gap of approximately 20 μm. The electrodewas a circular ITO electrode with an area of 1.13 cm² and a guard ring.The orientation layers were lecithin for homeotropic orientation (ε∥)and polyimide AL-1054 from Japan Synthetic Rubber for homogeneousorientation (ε_(⊥)). The capacities were determined with a frequencyresponse analyser Solatron 1260 using a sine wave with a voltage of 0.3V_(rms). The light used in the electro-optical measurements was whitelight. The set up used was commercially available equipment of AutronicMelchers, Germany. The characteristic voltages have been determinedunder perpendicular observation. The threshold (V₁₀)-mid grey (V₅₀)- andsaturation (V₉₀) voltages have been determined for 10%, 50% and 90%relative contrast, respectively.

The liquid crystal media according to the present invention can containfurther additives and chiral dopants in usual concentrations. The totalconcentration of these further constituents is in the range of 0% to10%, preferably 0.1% to 6%, based on the total mixture. Theconcentrations of the individual compounds used each are preferably inthe range of 0.1% to 3%. The concentration of these and of similaradditives is not taken into consideration for the values and ranges ofthe concentrations of the liquid crystal components and compounds of theliquid crystal media in this application.

The inventive liquid crystal media according to the present inventionconsist of several compounds, preferably of 3 to 30, more preferably of4 to 20 and most preferably of 4 to 16 compounds. These compounds aremixed in a conventional way. As a rule, the required amount of thecompound used in the smaller amount is dissolved in the compound used inthe greater amount. In case the temperature is above the clearing pointof the compound used in the higher concentration, it is particularlyeasy to observe completion of the process of dissolution. It is,however, also possible to prepare the media by other conventional ways,e.g., using so called pre-mixtures, which can be, e.g., homologous oreutectic mixtures of compounds or using so called multi-bottle-systems,the constituents of which are ready to use mixtures themselves.

By addition of suitable additives, the liquid crystal media according tothe instant invention can be modified in such a way, that they areusable in all known types of liquid crystal displays, either using theliquid crystal media as such, like TN-, TN-AMD, ECB-AMD, VAN-AMD, IPSand OCB LCDs and in particular in composite systems, like PDLC, NCAP, PNLCDs and especially in ASM-PA LCDs.

The melting point T(C,N), the transition from the smectic (S) to thenematic (N) phase T(S,N) and the clearing point T(N,I) of the liquidcrystals are given in degrees centigrade.

The storage stability in the bulk (LTS_(bulk)) of the inventive media ata given temperature T is determined by visual inspection. 2 g of themedia of interest are filled into a closed glass vessel (bottle) ofappropriate size placed in a refrigerator at a predeterminedtemperature. The bottles are checked every 24 h for the occurrence ofsmectic phases and of crystallisation. For every material and at eachtemperature two bottles are stored. If a crystallisation or theappearance of a smectic phase is observed in at least one of the twocorrespondent bottles the test is terminated and the time of the lastinspection before the one at which the occurrence of a higher orderedphase is observed is recorded as the respective storage stability.

For the determination of the storage stability in LC cells (LTS_(cell))of the inventive media at a given temperature T, the media are filledinto TN-type LC test cells with a orientation layers and having anapproximate surface area of 3 cm², an electrode area of about 3 cm² anda cell gap of 6 μm. The cells have no spacers in the area covered by theLC. Only in the edge seal spacers are used. The cells are sealed,polarizers are attached to the cells and the cells are and placed in acold box with a window and internal lighting at a predeterminedtemperature refrigerator. Generally three cells each are filled with agiven LC for each temperature investigated. The cells inside the coolbox are inspected visually through a window every 24 h for theoccurrence of smectic phases and of crystallization. Here too, the timeof the last inspection before the one at which the occurrence of ahigher ordered phase is observed in the first one of a given set of testcells is recorded as the respective storage stability.

For the so called “seed” test 1 g each of the respective mixtures ofinterest are kept at a temperature of 20° C. in bulk and subsequentlydoped with a tiny seed crystal of PUQU-2-F (1 to 10 mg), stored for 96 hat a temperature of 20° C. Then the sample is investigated by visualinspection whether the volume of the crystal has increased or whether ithas been unchanged or even decreased. Then the remaining nematic liquidcrystalline mixture is analyzed by GC-MS and its composition is comparedto that of the respective bulk material prior to doping.

Preferably, the liquid crystalline media according to the instantinvention comprise,

one or more compounds of formula Ia-4 and/or

one or more compounds of formula II, preferably of formula II-2 and mostpreferably selected from the group of sub-formulae II-2a-2 and II-2d-1and/or

one or more compounds of formula III, preferably of formula III-2 andmost preferably selected from the group of sub-formulae III-2f-3,III-2f-4 and III-2f-5 and/or

one or more compounds of formula IV-1, preferably of sub-formula IV-1band/or

one or more compounds of formula VI, preferably of sub-formulae VI-2.

The entire disclosures of all applications, patents and publications,cited herein and of corresponding European application No. 06005479.8,filed Mar. 17, 2006, are incorporated by reference herein.

In the present application and especially in the following examples, thestructures of the liquid crystal compounds are represented byabbreviations also called acronyms. The transformation of theabbreviations into the corresponding structures is straight forwardaccording to the following two tables A and B. All groups C_(n)H_(2n+1)and C_(m)H_(2m+1) are straight chain alkyl groups with n and m C-atoms,respectively. The interpretation of table B is self-evident. Table Adoes only list the abbreviations for the cores of the structures. Theindividual compounds are denoted by the abbreviation of the corefollowed by a hyphen and a code specifying the substituents R¹, R², L¹and L² follows: Code for R¹, R², L¹, L² R¹ R² L¹ L² nm C_(n)H_(2n+1)C_(m)H_(2m+1) H H nOm C_(n)H_(2n+1) OC_(m)H_(2m+1) H H nO.mOC_(n)H_(2n+1) C_(m)H_(2m+1) H H n C_(n)H_(2n+1) CN H H nN.FC_(n)H_(2n+1) CN H F nN.F.F C_(n)H_(2n+1) CN F F nF C_(n)H_(2n+1) F H HnF.F C_(n)H_(2n+1) F H F nF.F.F C_(n)H_(2n+1) F F F nOF OC_(n)H_(2n+1) FH H nCl C_(n)H_(2n+1) Cl H H nCl.F C_(n)H_(2n+1) Cl H F nCl.F.FC_(n)H_(2n+1) Cl F F nCF₃ C_(n)H_(2n+1) CF₃ H H nCF₃.F C_(n)H_(2n+1) CF₃H F nCF₃.F.F C_(n)H_(2n+1) CF₃ F F nOCF₃ C_(n)H_(2n+1) OCF₃ H H nOCF₃.FC_(n)H_(2n+1) OCF₃ H F nOCF₃.F.F C_(n)H_(2n+1) OCF₃ F F nOCF₂C_(n)H_(2n+1) OCHF₂ H H nOCF₂.F C_(n)H_(2n+1) OCHF₂ H F nOCF₂.F.FC_(n)H_(2n+1) OCHF₂ F F nS C_(n)H_(2n+1) NCS H H nS.F C_(n)H_(2n+1) NCSH F nS.F.F C_(n)H_(2n+1) NCS F F rVsN C_(r)H_(2r+1)—CH═CH—C_(s)H_(2s)—CN H H rEsN C_(r)H_(2r+1)—O—C_(s)H_(2s)— CN H H nAm C_(n)H_(2n+1)COOC_(m)H_(2m+1) H H

TABLE A

TABLE B

The liquid crystal media according to the instant invention containpreferably

-   -   seven or more, preferably eight or more compounds, preferably of        different formulae, selected from the group of compounds of        tables A and B and/or    -   one or more, more preferably two or more, preferably three or        more compounds, preferably of different formulae, selected from        the group of compounds of table A and/or    -   three or more, more preferably four or more compounds, more        preferably five or more compounds, preferably of different        formulae, selected from the group of compounds of table B.

EXAMPLES

The examples given in the following are illustrating the presentinvention without limiting it in any way.

However, the physical properties compositions illustrate to the expert,which properties can be achieved and in which ranges they can bemodified. Especially the combination of the various properties, whichcan be preferably achieved, is thus well defined for the expert.

Example 1

A liquid crystal mixture is realized with the composition and propertiesgiven in the following table. Composition Compound No. AbbreviationConc./% 1 GGP-3-CL 6.0 2 PGU-2-F 5.0 3 PGU-3-F 5.0 4 PUQU-3-F 6.0 5CC-3-V 33.0 6 CC-3-V1 9.0 7 CCP-V-1 19.0 8 PGP-2-3 7.0 9 PGP-2-4 7.0 10 GP-2-CL 3.0 Σ 100.0 Physical Properties T(N, I) = 74.0 ° C. n_(e) (20°C., 589.3 nm) = 1.6207 Δn (20° C., 589.3 nm) = 0.1238 ε|| (20° C., 1kHz) = 7.1 Δε (20° C., 1 kHz) = 4.0 γ₁ (20° C.) = 54 mPa · s LTS_(bulk)(−20° C.) = 1.000 h LTS_(bulk) (−30° C.) = 576 h V₁₀ (20° C.) = 2.06 VV₉₀ (20° C.) = 3.05 V

This mixture has favourable physical properties, e.g., of Δn,characteristic voltages and a moderately low rotational viscosity. Thus,it is equally well suited for displays operating in the TN mode. Itfurther has an excellent stability in the nematic phase at a temperatureof −30° C.

Comparative Example 2

A liquid crystal host mixture is realized with the composition andproperties given in the following table. Composition Compound No.Abbreviation Conc./% 1 PUQU-2-F 7.0 2 PUQU-3-F 15.0 3 CC-3-V 55.0 4PGP-2-3 4.0 5 PGP-2-4 3.0 6 CBC-33 3.0 7 CBC-33F 4.0 8 CBC-53 3.0 9CBC-53F 3.0 10  CBC-55F 3.0 Σ 100.0 Physical Properties T(N, I) = 74.7 °C. n_(e) (20° C., 589.3 nm) = 1.5844 Δn (20° C., 589.3 nm) = 0.0989 ε||(20° C., 1 kHz) = 7.7 Δε (20° C., 1 kHz) = 4.7 γ₁ (20° C.) = 67 mPa · sV₁₀ (20° C.) = 1.90 V V₉₀ (20° C.) = 2.78 V

This mixture in bulk is kept at a temperature of 20° C. and doped with atiny seed crystal of PUQU-2-F, stored for 96 h at a temperature of 20°C. and then the remaining nematic liquid crystalline mixture analyzed byGC-MS.

The results are shown for comparison in the following table togetherwith those of example 2

Example 2 Examples 2.1 and 2.2

To the mixture of comparative example 2, alternatively 2% and 5% ofGP-2-CL are added, and the respective mixtures are examined.

The results are shown in the following table. Example Compar. Ex. 2 2.12.2 Compound Composition Change No. Abbreviation Conc./Conc.₀ 1 PUQU-2-F0.88 0.97 1.00 2 PUQU-3-F 0.95 0.99 1.00 3 CC-3-V 1.01 1.00 1.00 4PGP-2-3 1.02 1.01 1.00 5 PGP-2-4 1.02 1.01 1.00 6 CBC-33 1.02 1.01 1.007 CBC-33F 1.02 1.01 1.00 8 CBC-53 1.02 1.01 1.00 9 CBC-53F 1.02 1.011.00 10 CBC-55F 1.02 1.01 1.00 11 GP-2-CL n.p. 1.00 1.00Remark:n.p.: not present

Comparative Example 3

A liquid crystal host mixture is realized with the composition andproperties given in the following table. Composition Compound No.Abbreviation Conc./% 1 GGP-3-CL 1.5 2 PUQU-2-F 11.0 3 PUQU-3-F 11.0 4CGU-2-F 3.0 5 CCGU-3-F 6.0 6 CCZU-3-F 12.0 7 CCQU-3-F 6.0 8 CC-3-V1 11.09 CC-5-V 16.5 10  CCP-V-1 12.0 11  CCP-V2-1 10.0 Σ 100.0 PhysicalProperties T(N, I) = 90.1 ° C. n_(e) (20° C., 589.3 nm) = 1.5830 Δn (20°C., 589.3 nm) = 0.0999 ε|| (20° C., 1 kHz) = 13.6 Δε (20° C., 1 kHz) =10.0 γ₁ (20° C.) = 100 mPa · s ν (20° C.) = 15 mm²s⁻¹ ν (−20° C.) = 210mm²s⁻¹ ν (−30° C.) = 4.000 mm²s⁻¹

This mixture in bulk is kept at a temperature of 20° C. and doped with atiny seed crystal of PUQU-2-F, stored for 96 h at a temperature of 20°C. and then the remaining nematic liquid crystalline mixture analyzed byGC-MS.

The results are shown for comparison in the following table togetherwith those of example 3.

Example 3 Examples 3.1 and 3.2

To the mixture of comparative example, alternatively 2% and 5% ofGP-2-CL are added, and the respective mixtures are examined.

The results are shown in the following table. Example Compar. Ex. 3 3.13.2 Compound Composition Change No. Abbreviation Conc./Conc.₀ 1 GGP-3-CL1.05 1.03 1.01 2 PUQU-2-F 0.70 0.80 0.94 3 PUQU-3-F 0.86 0.91 0.98 4CGU-2-F 1.04 1.03 1.01 5 CCGU-3-F 1.05 1.03 1.01 6 CCZU-3-F 1.05 1.031.01 7 CCQU-3-F 1.04 1.03 1.01 8 CC-3-V1 1.04 1.03 1.01 9 CC-5-V 1.041.03 1.01 10 CCP-V-1 1.05 1.03 1.01 11 CCP-V2-1 1.05 1.03 1.01 12GP-2-CL n.p. 1.03 1.01Remark:n.p.: not present

Example 4

A liquid crystal mixture is realized with the composition and propertiesgiven in the following table. Composition Compound No. AbbreviationConc./% 1 APUQU-2-F 8.0 2 PGU-2-F 7.0 3 PUQU-2-F 7.0 4 PUQU-3-F 8.0 5CDU-2-F 5.0 6 CC-3-V 26.0 7 CC-3-V1 12.5 8 CCP-V-1 12.0 9 CCP-V2-1 12.510  GP-2-CL 2.0 Σ 100.0 Physical Properties T(N, I) = 73.0 ° C. n_(e)(20° C., 589.3 nm) = 1.5856 Δn (20° C., 589.3 nm) = 0.0989 ε|| (20° C.,1 kHz) = 12.0 Δε (20° C., 1 kHz) = 8.50 γ₁ (20° C.) = 63 mPa · s k₁ (20°C.) = 11.7 pN k₃/k₁ (20° C.) = 1.14 LTS_(cell) (−20° C.) = 1.000 hLTS_(cell) (−30° C.) = 1.000 h V₀ (20° C.) = 1.24 V

This mixture has a favourably low value of Δn, a high value of Δε and alow rotational viscosity. Thus it is very well suited for displaysoperating in the IPS mode. It further has a good stability of thenematic phase at deep temperatures.

Example 5

A liquid crystal mixture is realized with the composition and propertiesgiven in the following table. Composition Compound No. AbbreviationConc./% 1 APUQU-2-F 9.0 2 PGU-2-F 8.0 3 PUQU-3-F 19.5 4 CCP-2OCF3 2.0 5CCP-3OCF3 8.0 6 CDU-2-F 1.5 7 CC-3-V 15.0 8 CC-3-V1 12.0 9 CCP-V-1 12.010  CCP-V2-1 11.0 11  GP-2-CL 2.0 Σ 100.0 Physical Properties T(N, I) =79.0 ° C. n_(e) (20° C., 589.3 nm) = 1.5965 Δn (20° C., 589.3 nm) =0.1096 ε|| (20° C., 1 kHz) = 14.7 Δε (20° C., 1 kHz) = 11.0 γ₁ (20° C.)= 80 mPa · s k₁ (20° C.) = 12.5 pN k₃/k₁ (20° C.) = 1.12 LTS_(cell)(−20° C.) = 1.000 h LTS_(cell) (−30° C.) = 1.000 h V₀ (20° C.) = 1.12 V

This mixture has a favourably low value of Δn, a high value of Δε and alow rotational viscosity. Thus it is very well suited for displaysoperating in the IPS mode. It further has a good stability of thenematic phase at deep temperatures.

The preceding examples can be repeated with similar success bysubstituting the generically or specifically described reactants and/oroperating conditions of this invention for those used in the precedingexamples.

Without further elaboration, it is believed that one skilled in the artcan, using the preceding description, utilize the present invention toits fullest extent. The preceding preferred specific embodiments are,therefore, to be construed as merely illustrative, and not limitative ofthe remainder of the disclosure in any way whatsoever.

From the foregoing description, one skilled in the art can easilyascertain the essential characteristics of this invention and, withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various usages andconditions.

1. A liquid crystal medium comprising: a first dielectrically positivecomponent, component A, comprising at least one dielectrically positivecompound of formula I

wherein R¹ is alkyl having 1 to 7 C-atoms, alkoxy having 1 to 7 C-atoms,fluorinated alkyl having 1 to 7 C-atoms, fluorinated alkoxy having 1 to7 C-atoms, alkenyl having 2 to 7 C-atoms, alkenyloxy having 2 to 7C-atoms, alkoxyalkyl having 2 to 7 C-atoms, or fluorinated alkenylhaving 2 to 7 C-atoms, X¹ is halogen, L are independently of each other,Cl or F, and n and m are, independently of each other, each an integerfrom 0 to 4; a second dielectrically positive component, component B,comprising one or more dielectrically positive compounds having adielectric anisotropy of more than 3; and optionally a dielectricallyneutral component, component C, comprising one or more dielectricallyneutral compounds having a dielectric anisotropy of −1.5 to
 3. 2. Aliquid crystal medium according to claim 1, wherein the concentration ofthe component A in the medium is 0.1% to 20%.
 3. A liquid crystal mediumaccording to at least one of claims 1 and 2, wherein the dielectricallypositive component, component B, comprises one or more compoundsselected from formulae II and III

wherein R² and R³ are, independently of each other, alkyl having 1 to 7C-atoms, alkoxy having 1 to 7 C-atoms, fluorinated alkyl having 1 to 7C-atoms, fluorinated alkoxy having 1 to 7 C-atoms, alkenyl having 2 to 7C-atoms, alkenyloxy having 2 to 7 C-atoms, alkoxyalkyl having 2 to 7C-atoms, or fluorinated alkenyl having 2 to 7 C-atoms,

to are, independently of each other,

L²¹, L²², L³¹ and L³² are, independently of each other, H or F, X² andX³ are, independently of each other, halogen, halogenated alkyl having 1to 3 C-atoms, alkoxy having 1 to 3 C-atoms, halogenated alkenyl having 2to 3 C-atoms, or alkenyloxy having 2 or 3 C-atoms, Z³ is —CH₂CH₂—,—CF₂CF₂—, —COO—, trans- —CH═CH—, trans- —CF═CF—, —CH₂O— or a singlebond, and l, m, n and o are, independently of each other, 0 or
 1. 4. Aliquid crystal medium according to claim 3, wherein said mediumcomprises one or more compounds of formula II.
 5. A liquid crystalmedium according to at least one of claims 3 to 4, wherein said mediumcomprises one or more compounds of formula III.
 6. A liquid crystalmedium according to at least one of claims 1 to 5, wherein said mediumcomprises one or more dielectrically neutral compounds of formula IV

wherein R⁴¹ and R⁴² , are, independently of each other, alkyl having 1to 7 C-atoms, alkoxy having 1 to 7 C-atoms, fluorinated alkyl having 1to 7 C-atoms, fluorinated alkoxy having 1 to 7 C-atoms, alkenyl having 2to 7 C-atoms, alkenyloxy having 2 to 7 C-atoms, alkoxyalkyl having 2 to7 C-atoms, or fluorinated alkenyl having 2 to 7 C-atoms,

independently of each other, and in case

is present twice, also these, independently of each other, are

Z⁴¹ and Z⁴² are, independently of each other, and in case Z⁴¹ is presenttwice, also these independently of each other, —CH₂CH₂—, —COO—, trans-—CH═CH—, trans- —CF═CF—, —CH₂O—, —CF₂O— or a single bond, and p is 0, 1or
 2. 7. A liquid crystal medium according to at least one of claims 1to 6, wherein said medium comprises one or more compounds of formula V

wherein R⁶¹ and R⁶², independently of each other are alkyl having 1 to 7C-atoms, alkoxy having 1 to 7 C-atoms, fluorinated alkyl having 1 to 7C-atoms, fluorinated alkoxy having 1 to 7 C-atoms, alkenyl having 2 to 7C-atoms, alkenyloxy having 2 to 7 C-atoms, alkoxyalkyl having 2 to 7C-atoms, or fluorinated alkenyl having 2 to 7 C-atoms,

and in case it is occurring twice in each occurrence independently ofeach other, is

Z⁶¹ and Z⁶² are, independently of each other, and in case Z⁶¹ is presenttwice, also these independently of each other, —CH₂CH₂—, —COO—, trans-—CH═CH—, trans- —CF═CF—, —CH₂O—, —CF₂O— or a single bond, and r is 0, 1or
 2. 8. A liquid crystal medium according to any one of claims 1 to 7,wherein component A comprises one or more compounds of formula Ia

wherein one of L¹¹ and L¹² is F and the other one is H.
 9. A liquidcrystal medium according to claim 8, wherein said one or more compoundsof formula Ia are selected from sub-formulae Ia-1 to Ia-4


10. A liquid crystal medium according to claim 9, wherein said one ormore compounds of formula Ia are selected from sub-formulae Ia-1 to Ia-4


11. A liquid crystal medium according to claim 4, wherein said one ormore compounds of formula II are selected from formulae II-1 and II-2

wherein L²³ and L²⁴ are, independently, H or F.
 12. A liquid crystalmedium according to claim 11, wherein L²¹ and L²² are each F, L³¹ andL³² are each F, or L²¹, L²², L³¹ and L³² are all F.
 13. A liquid crystalmedium according to claim 11, wherein component B comprises one or morecompounds of formula II-1, and said one or more compounds of formulaII-1 are selected from the compounds of formulae II-1a to II-1i


14. A liquid crystal medium according to claim 13, wherein L²¹ and L²²are each F, L³¹ and L³² are each F, or L²¹, L²², L³¹ and L³² are all F.15. A liquid crystal medium according to claim 11, wherein component Bcomprises one or more compounds of formula II-2, and said one or morecompounds of formula II-1 are selected from the compounds of formulaeII-2a to II-2d


16. A liquid crystal medium according to claim 15, wherein L²¹ and L²²are both F and L³¹ and L³² are both H, or L²¹, L²², L³¹ and L³² are allF.
 17. A liquid crystal medium according to claim 5, wherein said one ormore compounds of formula III are selected from formulae III-1 and III-2


18. A liquid crystal medium according to claim 17, wherein component Bcomprises one or more compounds of formula III-1, and said on or morecompounds of formula III-1 are selected from formulae III-1a and III-1b

wherein L³³ and L³⁴ are, independently, H or F.
 19. A liquid crystalmedium according to claim 17, wherein component B comprises one or morecompounds of formula III-2, and said one or more compounds of formulaIII-2 are selected from formulae III-2a to III-2h


20. In a liquid crystal display comprising a liquid crystal mediumwherein said medium is a medium according to at least one of claims 1 to19.
 21. A liquid crystal display according to claim 20, wherein saidmedium is addressed by an active matrix.
 22. In a method of generatingan electro-optical effect using a liquid crystal display, theimprovement wherein said display is a display according to claim 20.